Cellulosics sanitized through reaction with triazone substituted with biologically active quaternary ammonium salt



United States Patent 3,437 419 CELLULOSICS SANITIZEfi THROUGH REACTIONWITH TRIAZONE SUBSTITUTED WITH BIO- LOGICALLY ACTIVE QUATERNARY AMMONI-UM SALT Sidney Cohen, Fair Lawn, and Edward Grifiin Shay, Belle Mead,N.J., assignors to Millmaster Onyx Corporation,

New York, N.Y., a corporation of New York No Drawing. Filed Jan. 18,1965, Ser. No. 426,422 Int. Cl. A61l13/00, 1/00; D06m 11/00 U.S. Cl.8116.3 7 Claims This invention relates to durable microbicidal agentsfor cloth, paper and other fabrics or the fibers from which they areconstructed.

An object of the invenion is to synthesize antimicrobial compounds of anature suitable for application to such materials.

Another object of the invention is to apply the said antimicrobialagents to the fibers in such manner as to fix them thereon so as toresist depletion of the said agents by repeated laundering ordry-cleaning.

A further object of the invention is to obtain fabrics or fibers whichare self-sanitizing; that is to say, which will prevent the propagationof microorganisms thereon, and which will kill microorganisms with whichthey may become contaminated by air-borne matter, or upon being worn inthe form of garments, or by handling or by other means.

The agents with which the above objects can be accomplished are of theclass of thermosetting cyclic organic compounds of the triazinone type,containing as a part of their structure a germicidally potent quaternaryammonium salt of an integral acid group. These triazinones are derivedfrom 1,3 dimethylol tetrahydro-s-triazin-Z-one which contains in the-position a radical having a terminal acidic group.

They conform, in general, to the following structure:

wherein R is an aliphatic, alicyclic or aromatic radical bearing theresidue of an acidic group such as carboxylic, sulfonic, sulfuric,phosphoric and the like, and Z is the cation of a quaternary ammoniumsalt.

Triazinones are well known to the art, and may be prepared by reactingurea, an aldehyde and a primary amine. A typical preparation isdescribed in Self-Smoothing Fabrics, by J. T. Marsh, p. 77 (Chapman andHall Ltd., 1962). Triazinones containing an acid radical have also beendescribed as Well as their silver, mercurial and other metal salts.

Germicidal quaternary ammonium salts such as the halides have been foundto be substantive to cloth, and particularly to cellulosic fabrics,which are thereby rendered self-sanitizing. Ordinary laundering,however, removes the germicide in one or, at most, a very few washingswith either soap or synthetic detergents.

We have now found that we can render a fabric durably self-sanitizingand that this antibacterial effect persists after repeated launderings,by treating it with a quaternary triazinone compound having thestructure described above,

and heating it in the presence of a suitable acidic catalyst to fix thetriazinone to the cellulose by cross-linking.

Triazinone salts of this type may be prepared by heating urea andformaldehyde or other aldehyde with the alkali-metal salts of organicacids containing a primary amino group such as glycine, aminobutyricacid, sulfanilic acid, aminobenzoic acid and the like. The correspondingmicrobicidal quaternary ammonium salts may then be prepared bymetathesis. Upon reacting them in solution with quaternary ammoniumhalides or other suitable salts, the quaternary ammonium triazinonesalts separate out as a liquid or a solid phase which can be thusisolated and, if desired, further purified; however, suchafter-treatment is usually unnecessary.

Alternatively, a quaternary ammonium hydroxide or salt may be reactedwith an amino-substituted acid or its alkali-metal salt to yield thequaternary ammonium amino-substittued organic salt which can besegregated as described in pending applications, Ser. Nos. 323,598 and357,281, filed on Nov. 12, 1963 and Apr. 3, 1964, respectively, nowPatent Nos. 3,299,073 and 3,361,792, respectively. The resultant aminocompound may then be reacted with urea and formaldehyde to form thecorresponding substituted triazinone, or with dimethylol urea to formthe triazinone compound unsubstituted in the 1,3- positions which maythen be further reacted with formaldehyde to form the1,3-dimethy1o1triazinone compound.

Typical examples of the quaternary ammonium compounds which may be usedin this invention are the alkyl trimethyl ammonium chlorides,alkyl-benzyl trimethyl ammonium chlorides, alkyl dimethyl benzylammonium chlorides, alkyl dimethyl menaphthyl ammonium chlorides, alkyldimethyl substituted-benzyl ammonium chlorides in which the benzylradical is substituted with one or more side chains containing from 1 to5 carbon atoms such, for example, as methyl, dimethyl, ethyl and thelike and in which the carbon atoms may all be in the same or dilferoutside chains or in which the benzyl radical bears one, two or morehalogen atoms such as chlorine or bromine, alkyl pyridinium chlorides,alkyl isoquinolinium chlorides and bromides, alkyl lower-alkylpyrrolidinium chlorides, alkyl lower-alkyl morpholinium chlorides in allof which the alkyl group may have from 8 to 22 carbon atoms and thelower-alkyl group may have from 1 to 4 carbon atoms and alkyl phenoxyethoxy ethyl dimethyl benzyl ammonium chloride in which the akyl radicalmay be iso-octyl or nonyl and in which the phenyl radical may, ifdesired, be substituted by a methyl radical. Various other analogs ofthese quaternaries may also be employed such, for example, as cetyldimethyl ethyl ammonium bromide or oleyl dimethyl ethyl ammoniumbromide.

In general, the quaternary ammonium compounds useful in this inventionare the higher alkyl quaternary ammonium hydroxides, halides (chloridesand bromides), sulfates, methosulfates and the like possessing thefollowing formula:

where R is an alkyl or alkaralkyl radical containing from 8 to 22 carbonatoms or an alkyl phenoxy ethoxy ethyl radical in which R is an alkylradical containing from 8 to 9 carbon atoms and in which the phenylradical may be substituted by a methyl group; R and R are methyl orethyl radicals or members of a heterocyclic ring system such aspyridine, isoquinoline, pyrrolidine and morpholine; R' is a methylradical or a benzyl group or a substituted-benzyl group such, forexample, as a monochlorobenzyl radical or a dichlorobenzyl radical ormixture thereof or a methyl benzyl, dimethyl benzyl, ethyl benzyl,diethyl benzyl, isopropyl benzyl, tertiary butyl benzyl or anotherbenzyl radical containing from 1 to carbon atoms as side chains, eitheras a single side chain or a multiplicity of side chains includingmixtures thereof or a menaphthyl group or hydrogenated menaphthyl group.When R and R are members of a morpholine or pyrrolidine ring, R is amethyl, ethyl, propyl or butyl group. When R and R are members of anunsaturated heterocyclic ring such as pyridine or isoquinoline, R' isthe same radical as R". X in the above formula corresponds to a halideradical such as chloride, bromide or iodide or to any otherwater-soluble anion such as methosulfate.

'In general, we prefer to use such quaternary ammonium compounds whichhave a phenol coeflicient of at least 100 with respect to bothStaphylococcus aureus and Salmonella typhosa at 20 C. when determined bythe standard method given in the Ofiicial Methods of Analysis of theAssociation of Ofiicial Agricultural Chemists, ninth edition (1960), p.63 et seq.

The following examples of methods of preparing, applying and testing theintermediates and the products of this invention are illustrative only,and are not to be considered as limiting the invention, which may bemodified or varied within the spirit and scope of the claims.

Example I One mol of urea was dissolved in 400 grams or 3.2 mols offormalin solution in a three-neck flask fitted with an agitator, areflux condenser and a dropping funnel. The temperature thereupon fellto C. A solution of 75 grams of 0.6 mol of taurine (2-aminoethanesulfonic acid), 60 grams of water and 48 grams or 0.6 mol of 50% sodiumhydroxide solution was charged into the dropping funnel, whence it wasadded gradually to the agitated urea-formaldehyde solution. Anexothermic reaction occurred. The reaction was continued for one hourunder reflux at about 95 C. until the reaction was essentially completeand the free formaldehyde content was less than 1%. The productcontained 0.6 mol of 1,3- dimethylol-tetr'ahydro 5 (sodiumsulfoethyl)-s-triazin- 2-one, at a concentration of about 35%. Aftercooling, the solution was clarified by filtration through paper.

Example II The reaction according to Example I was carried out withoutexcess of urea and formaldehyde. A solution of sodium tauride wasprepared by dissolving 125 grams or 1 mol of 2-aminoethane sulfonic acidand 80 grams of 1 mol of 50% sodium hydroxide solution in 400 grams ofwater. This solution was added gradually to a solution of 60 grams of 1mole of urea in 324 grams or 4 mols of Formalin solution, withagitation, and at about 60 C. The reaction mixture was then heated atthe refluxing temperature for one hour until the free formaldehydecontent was 1.45%. The product, 1,3-dimethylol-tetrahydro- S-(sodiumsulfoethyl)-s-triazin-2-one of molecular weight 291, was obtained in 30%concentration.

Example III By substituting 173 grams or 1 mol of sulfanilic acid forthe taurine of Example II, and conducting the reaction in a similarmanner until the residual formaldehyde content was 2.9%, a 30% solutionof 1,3-dimethy1ol-tetrahydro-S-(sodium p-sulfophenyl)-s-triazin-2-one ofmolecular weight 339 was obtained.

Example IV A solution containing 1 mol of sodium m-aminobenzoate wasprepared by dissolving 137 grams of m-benzoic acid in 181 grams of waterand 80 grams of 50% sodium hydroxide. This was reacted as in Example IIwith 60 A 40% solution of 1,3-dimethylol-tetrahydro-S-(sodiumcarboxymethyl)-s-triazin-2-one of molecular weight 241 was prepared inthe manner of Example IV, substituting for the sodium aminobenzoate, 218grams of a solution containing 1 mol of sodium aminoacetate. Thefiltered product contained 2.8% of unreacted formaldehyde.

Example VI 200 grams of the product of Example I was reacted with anexcess of an aqueous solution of alkyl dimethyl ethylbenzyl ammoniumchloride (Onyx Chemical Corporations BTC 471 in which the alkyldistribution is 50% C 30% C 17% C 3% C The reaction mixture was shakenin a separatory funnel with 150 ml. of benzene, and the oily layer wasremoved and dried in a vacuum oven. The product assayed 51% of1,3-dimethylol-tetrahydro-S-(alkyl dimethyl ethyl-benzyl ammoniumsulfoethyl)-s-triazin-2-one, and 48% of alkyl dimethyl ethyl-benzylammonium chloride.

Example VII Without further purification, the product of Example VI wasapplied to x 80 cotton print cloth test fabric as follows:

A 2% aqueous solution of the crude product of Example VI, containing0.2% by weight of Onyx Chemical Corporations Catalyst ZM (a modifiedzinc nitrate catalyst containing 20% of zinc nitrate and an organicacid), was applied on a padder to about 75% wet pickup. This solutiontherefore contained 1% of the alkyl dimethyl ethyl-benzyl ammonium saltof the triazinone and 1% of the alkyl dimethyl ethyl-benzyl ammoniumchloride. For a control, the same test fabric was treated with a 1%solution of the alkyl dimethyl ethyl-benzyl ammonium chloride and 0.2%of the Catalyst ZM, applied in the same manner. Both swatches were driedfor 2 minutes at 220 F. and cured for 5 minutes at 300 F.

They were then laundered in an automatic washing machine of thehousehold type at 140 F. with Tide (Tide is the registered trademark ofthe Procter and Gamble Company) and dried in a tumble drier. Thisprocess was repeated for ten successive launderings.

The two swatches, and also two corresponding unlaundered swatches, weretested bacteriologically as follows, according to Tentative Test MethodNo. 100-1961 T of the Technical Manual of the American Association ofTextile Chemists and Colorists (1964):

The swatches were inoculated with Staphylococcus aureus according to therequirements of the test, the inoculum load being 214x 10* organisms.The samples were incubated at 37 C. for eighteen hours, after which theswatches were shaken with sterile distilled water. The suspensions werediluted serially and plated in tryptone glucose extract agar andincubated at 37 C. for forty-eight hours. The percentage reduction ofthe inoculum was calculated in the prescribed manner. A selfsanitizingactivity claim calls for a minimum reduction 10f in the number oforganisms which were inocuated.

Table I shows the number of organisms recovered; UCT=untreated controlfabric; A=unlaundered fabric treated with the product of Example VI andAW=the same after ten launderings; B=unlaundered fabric treated withalkyl dimethyl ethyl-benzyl ammonium chloride and BW=the same after tenlaunderings; TNC:too numerous to count.

TABLE I Organisms recovered Percent organisms killed 'INO Example VIIIExample IX 390 grams of the product of Example II was reacted with anequirnolar amount of an aqueous solution of alkyl dimethyl benzylammonium chloride (Onyx Chemical Corporations BTC 824 in which the alkyldistribution is 60% C14, 30% C C 5% C The reaction mixture was shaken ina separatory funnel along with a small quantity of benzene and theorganic product layer was separated and vacuum dried. The product, 1,3-dimethylol-tetrahydro-S-(alkyl dimethyl benzyl ammoniumsulfoethyl)-s-triazin-2-one, was recovered in 85% of the theoreticalyield.

Example X 296 grams of the product of Example 1V was reacted with amolecularly equivalent amount of an aqueous alcohol solution of alkylisoquinolinium bromide (Onyx Chemical Corporations Isothan Q-75 in whichthe alkyl distribution is 50% C 30% C 17% C 3% C The reaction mixturewas shaken in a separatory funnel with a little benzene and the organicproduct layer was removed and dried in a vacuum oven. The product, 1,3dimethylol tetrahydro-S-(alkylisoquinolinium-mcarboxyphenyl)-striazin-2-0ne, was recovered insubstantially the theoretical yield.

Example XI 390 grams of the product of Example V was reacted with anequimolar amount of a solution of the alkyl dimethyl benzyl ammoniumchloride of Example IX. The reaction mixture was shaken in a separatoryfunnel with a little benzene and the organic product layer was removedand dried in a vacuum oven. The product,Lil-dimethyloltetrahydro-S-(alkyl dimethyl benzyl ammoniumcarboxymethyl-s-triazin-Z-one, was recovered in 82% of the theoreticalyield.

The above examples demonstrate the preparation of triazinone compoundscontaining as an integral part of the molecule a microbicidally activequaternary ammonium group. They also demonstrate that these compounds,like the simpler triazinone compounds from which they are derived, canbe permanently aflixed to fabrics and especially to cellulosic fabricsby cross-linking, thus rendering the fabrics self-sanitizing.Furthermore, they show that the germicidal properties of the fabricpersist after repeated launderings.

Fabrics and fibers thus self-sanitized may be employed for a number ofuseful purposes, such as the preservation of the fibers themselves fromdecay, the prevention of cross-infection and of airor dust-borneinfection, the inhibition of odor-forming bacteria and, in general, thekilling or stasis of microorganisms which cause disease, putrefaction ordeterioration of materials. They find application in such articles asblankets, bedlinens, surgical dressings, hospital uniforms, air filters,curtains and draperies, upholstery stuffing and padding, diapers,undergarments, socks and the like.

We claim:

1. The process of sanitizing cellulosic materials which comprisestreating cellulosic material in the presence of an acidic catalyst m'tha triazinone compound having the structure 0 HOCHPN/ NCHzOH H H1 N R I Zwherein R is a radical selected from the group consisting of aliphatic,alicyclic and aromatic radicals bearing the residue of an acidic group,and Z is the cation of a microbiologically active quaternary ammoniumsalt.

2. The process of sanitizing cellulosic materials as defined in claim 1wherein the triazinone compound is 1,3- dimethylol-tetrahydro-S-(alkyldimethyl ethylbenzyl ammonium sulfoethyl)-s-triazin-2-one.

3. The process of sanitizing cellulosic materials as defined in claim 1wherein the triazinone compound as 1,3- dimethylol-tetrahydro-S-(alkyldimethyl ethylbenzyl ammonium-p-sulfoethyl) -s-triazin-2-one.

4. The process of sanitizing cellulosic materials as defined in claim 1wherein the triazinone compound is 1,3- dimethylol tetrahydro 5 (alkyldimethyl benzyl ammonium sulfoethyl)-s-triazin-2-one.

5. The process of sanitizing cellulosic materials as defined in claim 1wherein the triazinone compound is 1,3- dimethylol-tetrahydro-S-(alkylisoquinolinium-m-carboxyphenyl)-s-triazin-2-one.

6. The process of sanitizing cellulosic materials as defined in claim 1wherein the triazinone compound is 1,3- dimethylol-tetrahydro-S-(alkyldimethyl benzyl ammonium carboxymethyl)-s-triazin-2-one.

7. Cellulosic textile material cross-linked with a sanitizing agent bythe process as defined in claim 1, said material being resistant todepletion of said agent by repeated laundering or dry cleaning.

References Cited UNITED STATES PATENTS 2,763,574 9/1956 Ruperti 8-116.3X 3,002,859 10/ 1961 Hurwitz 8116.3 X 3,050,419 8/1962 Rupcrti 8-l16.3 X3,082,118 3/1963 Shaw ct al 8116.3 X 3,085,909 4/1963 Gogliardi ct al.81l6.3 X 3,130,193 4/1964 Shaw et al 8116.3 X 3,252,751 5/1966 Shaw eta1 8116.3 X 3,317,345 5/1967 Pluck et a1 8-116.3 X

NORMAN G. TORCHIN, Primary Examiner. J. CANNON, Assistant Examiner.

US. Cl. X.R.

U.S. DEPARTMENT OF COMMERCE PATENT OFFICE Washington, D.C. 20231 UNITEDSTATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,437,419April 8, 19

Sidney Cohen et al.

It is certified that error appears in the above identified patent andthat said Letters Patent are hereby corrected as shown below:

Column 3, line 52, "of", second occurrence, should read or line 5 "of,second occurrence, should read or Column 4, line 58, "214 x 10' shouldread 214 x 10 Column 6, line 32 "as" should read is line 34,"sulfoethyl" should read sulfophenyl Signed and sealed this 14th day ofApril 1970.

(SEAL) Attest:

WILLIAM E. SCHUYLER, JR.

Commissioner of Patents Edward M. Fletcher, 11'.

Attesting Officer

1. THE PROCESS OF SANITIZING CELLULOSIC MATERIALS WHICH COMPRISESTREATING CELLULOSIC MATERIAL IN THE PRESENCE OF AN ACIDIC CATALYST WITHA TRIAZINONE COMPOUND HAVING THE STRUCTURE